Toward RGB LEDs based on rare earth-doped ZnO.

By using ZnO thin films doped with Ce, Tb or Eu, deposited via radiofrequency magnetron sputtering, we have developed monochromatic (blue, green and red, respectively) light emitting devices (LEDs). The rare earth ions introduced with doping rates lower than 2% exhibit narrow and intense emission peaks due to electronic transitions in relaxation processes induced after electrical excitation. This study proves zinc oxide to be a good host for these elements, its high conductivity and optical transparency in the visible range being as well exploited as top transparent electrode. After structural characterization of the different doped layers, a device structure with intense electroluminescence is presented, modeled, and electrically and optically characterized. The different emission spectra obtained are compared in a chromatic diagram, providing a reference for future works with similar devices. The results hereby presented demonstrate three operating monochromatic LEDs, as well as a combination of the three species into another one, with a simply-designed structure compatible with current Si technology and demonstrating an integrated red-green-blue emission.

Enhanced photovoltaic performance of inverted polymer solar cells through atomic layer deposited Al2O3 passivation of ZnO-nanoparticle buffer layer.

In this work, an atomic layer deposited (ALD) Al2O3 ultrathin layer was introduced to passivate the ZnO-nanoparticle (NP) buffer layer of inverted polymer solar cells (PSCs) based on P3HT:PCBM. The surface morphology of the ZnO-NP/Al2O3 interface was systematically analyzed by using a variety of tools, in particular transmission electron microscopy (TEM), evidencing a conformal ALD-Al2O3 deposition. The thickness of the Al2O3 layers was optimized at the nanoscale to boost electron transport of the ZnO-NP layer, which can be attributed to the suppression of oxygen vacancy defects in ZnO-NPs confirmed by photoluminescence measurement. The optimal inverted PSCs passivated by ALD-Al2O3 exhibited an ∼22% higher power conversion efficiency than the control devices with a pristine ZnO-NP buffer layer. The employment of the ALD-Al2O3 passivation layer with precisely controlled thickness provides a promising approach to develop high efficiency PSCs with novel polymer materials.

Local Schottky contacts of embedded Ag nanoparticles in Al2O3/SiN x :H stacks on Si: a design to enhance field effect passivation of Si junctions.

This paper describes an original design leading to the field effect passivation of Si n+-p junctions. Ordered Ag nanoparticle (Ag-NP) arrays with optimal size and coverage fabricated by means of nanosphere lithography and thermal evaporation, were embedded in ultrathin-Al2O3/SiN x :H stacks on the top of implanted Si n+-p junctions, to achieve effective surface passivation. One way to characterize surface passivation is to use photocurrent, sensitive to recombination centers. We evidenced an improvement of photocurrent by a factor of 5 with the presence of Ag NPs. Finite-difference time-domain (FDTD) simulations combining with semi-quantitative calculations demonstrated that such gain was mainly due to the enhanced field effect passivation through the depleted region associated with the Ag-NPs/Si Schottky contacts.

Structural and emission properties of Tb3+-doped nitrogen-rich silicon oxynitride films.

Terbium doped silicon oxynitride host matrix is suitable for various applications such as light emitters compatible with CMOS technology or frequency converter systems for photovoltaic cells. In this study, amorphous Tb3+ ion doped nitrogen-rich silicon oxynitride (NRSON) thin films were fabricated using a reactive magnetron co-sputtering method, with various N2 flows and annealing conditions, in order to study their structural and emission properties. Rutherford backscattering (RBS) measurements and refractive index values confirmed the silicon oxynitride nature of the films. An electron microscopy analysis conducted for different annealing temperatures (T A) was also performed up to 1200 °C. Transmission electron microscopy (TEM) images revealed two different sublayers. The top layer showed porosities coming from a degassing of oxygen during deposition and annealing, while in the region close to the substrate, a multilayer-like structure of SiO2 and Si3N4 phases appeared, involving a spinodal decomposition. Upon a 1200 °C annealing treatment, a significant density of Tb clusters was detected, indicating a higher thermal threshold of rare earth (RE) clusterization in comparison to the silicon oxide matrix. With an opposite variation of the N2 flow during the deposition, the nitrogen excess parameter (Nex) estimated by RBS measurements was introduced to investigate the Fourier transform infrared (FTIR) spectrum behavior and emission properties. Different vibration modes of the Si-N and Si-O bonds have been carefully identified from the FTIR spectra characterizing such host matrices, especially the 'out-of-phase' stretching vibration mode of the Si-O bond. The highest Tb3+ photoluminescence (PL) intensity was obtained by optimizing the N incorporation and the annealing conditions. In addition, according to these conditions, the integrated PL intensity variation confirmed that the silicon nitride-based host matrix had a higher thermal threshold of rare earth clusterization than its silicon oxide counterpart. Analysis of time-resolved PL intensity versus T A showed the impact of Tb clustering on decay times, in agreement with the TEM observations. Finally, PL and PL excitation (PLE) experiments and comparison of the related spectra between undoped and Tb-doped samples were carried out to investigate the impact of the band tails on the excitation mechanism of Tb3+ ions.

Studies of non-vacuum processing of Cu-chalcogenide thin films.

Cu-chalcogenide thin films were prepared using a two stage method: one step electrodeposition of CuISe and CIGSe, and the sulfurisation of CISe to prepare CISSe thin films. The films were deposited on different substrates: Mo and ITO coated glass. The optimum potentials for electrodeposition of CISe and CIGSe films were respectively selected in the range -400 to -550 mV and -650 to -700 mV (vs. SCE). The electrodeposited layers were firmly adhesive. The well known chalcopyrite structure appears after annealing at 400 degrees C under Argon for CISe. The band gap value deduced from the optical measurements is close to 1 eV. To increase this value, addition of gallium in the aqueous electrolytic solution was performed. A band gap value as high as 1.26 eV was recorded on the obtained CIGSe films. Sulfurisation of CISe layers under 5% H2S/Ar atmosphere lead to a shift of the position of the principal XRD peaks indicating the substitution of selenium atoms by sulfur atoms and thus the formation of the quaternary CISSe. Optical measurements performed on this quaternary compound show that our films exhibit a band gap value scaling from 1 eV to 1.4 eV depending on the amount of sulphur incorporated into the layers during the heat treatments.

Thermal stability of high-k Si-rich HfO(2) layers grown by RF magnetron sputtering.

The microstructure and optical properties of HfSiO films fabricated by RF magnetron sputtering were studied by means of x-ray diffraction, transmission electron microscopy, spectroscopic ellipsometry and attenuated total reflection infrared spectroscopy versus annealing treatment. It was shown that silicon incorporation in the HfO(2) matrix plays an important role in the structure stability of the layers. Thus, the increase of the annealing temperature up to 1000 degrees C did not lead to the crystallization of the films. The evolution of the chemical composition as well as a decrease of the density of the films was attributed to the phase separation of HfSiO on HfO(2) and SiO(2) phases in the film. An annealing at 1000-1100 degrees C results in the formation of the multilayer Si-rich/Hf-rich structure and was explained by a surface-directed spinodal decomposition. The formation of the stable tetragonal structure of HfO(2) phase was shown upon annealing treatment at 1100 degrees C.

The nitrogen concentration effect on Ce doped SiOxNy emission: towards optimized Ce3+ for LED applications.

Ce-Doped SiOxNy films are deposited by magnetron reactive sputtering from a CeO2 target under a nitrogen reactive gas atmosphere. Visible photoluminescence measurements regarding the nitrogen gas flow reveal a large emission band centered at 450 nm for a sample deposited under a 2 sccm flow. Special attention is paid to the origin of such an emission at high nitrogen concentration. Different emitting centers are suggested in Ce doped SiOxNy films (e.g. band tails, CeO2, Ce clusters, Ce3+ ions), with different activation scenarios to explain the luminescence. X-ray photoelectron spectroscopy (XPS) reveals the exclusive presence of Ce3+ ions whatever the nitrogen or Ce concentrations, while transmission electron microscopy (TEM) shows no clusters or silicates upon high temperature annealing. With the help of photoluminescence excitation spectroscopy (PLE), a wide excitation range from 250 nm up to 400 nm is revealed and various excitations of Ce3+ ions are proposed involving direct or indirect mechanisms. Nitrogen concentration plays an important role in Ce3+ emission by modifying Ce surroundings, reducing the Si phase volume in SiOxNy and causing a nephelauxetic effect. Taking into account the optimized nitrogen growth parameters, the Ce concentration is analyzed as a new parameter. Under UV excitation, a strong emission is visible to the naked eye with high Ce3+ concentration (6 at%). No saturation of the photoluminescence intensity is observed, confirming again the lack of Ce cluster or silicate phase formation due to the nitrogen presence.

Impurity-Governed Modification of Optical and Structural Properties of ZrO2-Based Composites Doped with Cu and Y.

The influence of calcination temperature on copper spatial localization in Y-stabilized ZrO2 powders was studied by attenuated total reflection, diffuse reflectance, electron paramagnetic resonance, transmission electron microscopy, electron energy loss, and energy-dispersive X-ray spectroscopies. It was found that calcination temperature rise in the range of 500-700 °C caused the increase of copper concentration in the volume of ZrO2 nanocrystals. This increase was due to Cu in-diffusion from surface complexes that contained copper ions linked with either water molecules or OH groups. This copper in-diffusion led also to an enhancement of absorption band peaked at ~270 nm that was ascribed to the formation of additional oxygen vacancies in nanocrystal volume. Further increasing of calcination temperature from 800 up to 1000 °C resulted in outward Cu diffusion accompanied by a decrease of the intensity of the 270-nm absorption band (i.e., oxygen vacancies' number), the transformation of ZrO2 tetragonal (cubic) phase to monoclinic one as well as the enhancement of absorption band of dispersed and crystalline CuO in the 600-900 nm range.

In Situ Transmission Electron Microscopy Studies of the Magnetization Reversal Mechanism in Information Storage Materials.

: The Foucault and Fresnel modes of Lorentz microscopy, together with a quantitative magnetization mapping technique, summed image differential phase-contrast imaging, were used to study the magnetization reversal mechanism of the sense layer in spin-valve structures exhibiting the giant magnetoresistance effect. In addition to studies of sheet film, lithographically defined spin-valve elements were investigated. A current can be passed through the element during magnetizing so that the effect of the applied current on the giant magnetoresistance and magnetization reversal mechanism can be studied. Results are presented for a number of different spin-valve structures.

The role of atomic scale investigation in the development of nanoscale materials for information storage applications.

It is well established that the response of devices based on the giant magnetoresistance (GMR) effect depends critically on film microstructure, with parameters such as interfacial abruptness, the roughness and waviness of the layers, and grain size being crucial. Such devices have applications in information storage systems, and are therefore of great technological interest as well as being of fundamental scientific interest. The layers must be studied at high spatial resolution if the microstructural parameters are to be characterized with sufficient detail to enable the effects of fabrication conditions on properties to be understood, and the techniques of high resolution electron microscopy, transmission electron microscopy chemical mapping, and atom probe microanalysis are ideally suited. This article describes the application of these techniques to a range of materials including spin valves, spin tunnel junctions, and GMR multilayers.